CN103242158B - Technological method for synthesizing ethyl acetate - Google Patents
Technological method for synthesizing ethyl acetate Download PDFInfo
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- CN103242158B CN103242158B CN201310195417.3A CN201310195417A CN103242158B CN 103242158 B CN103242158 B CN 103242158B CN 201310195417 A CN201310195417 A CN 201310195417A CN 103242158 B CN103242158 B CN 103242158B
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Abstract
The invention relates to a novel technological method for synthesizing ethyl acetate. The novel technological method is characterized in that tower top vapor and tower bottom distillate are subjected to heat exchange to realize great energy coupling and save energy consumption by combining differential pressure thermal coupling with a reactive distillation dividing wall column technology and using a differential pressure thermal coupling technology as well as differential pressure operation between the tower top and the tower bottom of a dividing wall column, on the basis of simplifying the original flow and saving the equipment investment by using a dividing wall column technology.
Description
Technical field
The present invention relates to a kind of processing method of synthesizing ethyl acetate.
Background technology
Ethyl acetate (Ethyl Acetate, EA), also known as vinyl acetic monomer, is a branch of acetic acid downstream derivative product.It belongs to the category of chemical solvents, is a kind of important green organic solvent, has excellent solvability, quick-drying; Be compared with based on industrial raw material, mainly for the production of the solvent of coating, tamanori, ethyl cellulose, leatheroid, malthoid tinting material and regenerated fiber etc. in industry, also can be used as the production of tamanori for printing-ink, olivet etc., the production etc. of medicine, organic acid product is used for as extraction agent, can be used as producing the raw material of the fruit essence such as pineapple, banana, strawberry and whisky, milk wet goods spices in addition, purposes is very extensive, and development prospect is had an optimistic view of.Along with deepening constantly of China market economy, the continuous reinforcement of overall national strength, the standard of living of the people improves constantly, the consumption of people from eating, wear, consumption to transfers such as house, automobile, health.The increase to industry requirements such as coating, tackiness agent, medicine will be driven like this, and cause the demand of the vinyl acetic monomer product of one of raw material to increase.Due to the performance that it is special, ethyl acetate is quite active in world's Chemical market, and also causes the extensive concern of people to the research of its preparation technology and device aspect.
The method of production ethyl acetate in the world roughly has following several at present: acetate ethanol direct esterification, acetaldehyde condensation method, alcohol dehydrogenase method, ethene and acetic acid direct addition method, catalytic rectification process.The traditional technology of synthesizing ethyl acetate is the continuous esterification method production line using the vitriol oil of 98% as catalyzer, and acetic acid and ethanol carry out esterification in a kettle., generates ethyl acetate and water; The thick ester be obtained by reacting refines to obtain the finished product through rectifying tower.Due to strong inorganic acid catalyst usually can bring equipment corrosion, side reaction is many, postprocessing working procedures is loaded down with trivial details and the problem such as environmental pollution, now gradually by the liquid and solid phase reaction of solid acid catalyst (acidic cation-exchange resin, molecular sieve and solid super-strong acid) and gas-solid phase reaction substitute.
Reaction process and rectifying are organically coupled by reactive distillation hydrolysis process, make reactant while carrying out reacting and product separation, and enhanced hydrolysis reacts, and reduces facility investment and operation easier.Such as, patent CN1433395A proposes a kind of new device producing ethyl acetate, this device is under the existence of solid acid catalyst, ethanol and acetic acid or diacetyl oxide generation esterification generate ethyl acetate, form azeotrope at tower top and be separated into aqueous phase and ester phase, part ester refluxes mutually, and another part does product and extracts out.Reactive distillation processes disclosed in patent US8314266B2 then needs by esterification synthesizing ethyl acetate in one with reactor, and continues reaction in follow-up reactive distillation column, the purification realizing product be separated.Patent US0035390A1 proposes a kind of reaction distillation device of alcohol dehydrogenase, and at the continuous separating hydrogen gas of tower top, tower reactor loads the content that appropriate hydrogenation catalyst reduces butanone and butyraldehyde, and obtains the higher ethyl acetate product of purity.
Partition wall type reactive distillation tower technology is the integrated strengthening means of one next door tower technology and reactive distillation processes are coupled, the reaction of reactant and the purification of product are realized in same tower, on the basis ensureing original high conversion, significantly save facility investment.Such as, next door reactive distillation tower technology is applied on the hydrolysis process of methyl acetate by CN101357887, achieves good energy-saving effect.
Summary of the invention
It is high to there is temperature of reaction in acetate ethanol direct esterification, acetic acid utilization ratio is low, easily side reaction occurs, and product treatment difficulty, catalyzer are strong to equipment corrosion, the shortcomings such as waste liquor contamination environment and production cost are high, improved gradually or substitute by other advanced technologies.Although have solid acid catalyst or ion exchange resin etc. constantly to put into production as catalyzer, still there is certain difficulty in common reaction rectification method production ethyl acetate in facility investment and operational condition.The present invention is intended to introduce a kind of novel thermal coupling technique---and differential pressure heat is coupled, combine with reactive distillation next door tower technology, original flow process is simplified utilizing next door tower technology, save on the basis of facility investment, by differential pressure heat coupling technique, utilize the differential pressure at the bottom of next door column overhead and tower to operate, will make to distillate liquid phase at the bottom of overhead vapours and tower and complete heat exchange, realize significantly Energy Coupling, save energy consumption.
Processing method of the present invention comprises the following steps:
Step one: ethanol and acetic acid enter next door tower (C2) from the bottom of reaction zone (II),
Described next door tower (C2) comprises rectification zone (I), reaction zone (II) and side line rectification zone (III),
React with Zeo-karb in reaction zone (II) and generate ethyl acetate, the ethanol that the ethyl acetate generated washes away part water through rectification zone (I) and do not react completely, and obtain highly purified ethyl acetate product in side line rectification zone (III) bottom;
Step 2: next door tower (C2) tower top working pressure is 100 ~ 110kPa, service temperature is 60 ~ 75 DEG C, reaction bed temperature is 95 ~ 110 DEG C, still temperature is 115 ~ 120 DEG C, in step one, the tower top of another part water, the ethanol do not reacted completely and portion of ethyl acetate next door tower (C2) forms steam and enters rectifying tower (C1) through compressor (3) pressurization, for it provides upflowing vapor stream, realize the effect of reboiler;
Step 3: described rectifying tower (C1) working pressure is 500 ~ 650kPa, tower top service temperature is 120 ~ 130 DEG C, in rectifying tower (C1), the ethyl acetate generated and water and ethanol define binary, ternary azeotrope, constantly slough the ethyl acetate generated wherein through refinery distillation, obtain the heteroazeotrope stream close to ethyl acetate, water and ethanol at tower top;
Step 4: at the non-homogeneous mixture stream that rectifying tower (C1) tower top obtains in step 3, through the First Heat Exchanger (4) of next door tower (C2) and the second interchanger (5) and the heat exchange of next door tower (C2) tower base stream, again after auxiliary condenser (2) further cooling, aqueous phase and ester phase is divided in phase splitter (1), aqueous phase discharges system, ester squeezes into rectifying tower (C1) as backflow, discharging at the bottom of the tower of rectifying tower (C1) is that next door tower (C2) provides liquid-phase reflux, realizes the function of condenser.
2. the processing method of a kind of synthesizing ethyl acetate as claimed in claim 1, is characterized in that described reaction zone (I) feeding temperature is 20 ~ 80 DEG C, and the raw materials components mole ratio of acetic acid and ethanol is 1: 1 ~ 1.1: 1.
3. the processing method of a kind of synthesizing ethyl acetate as claimed in claim 1, is characterized in that described next door tower (C2) is 2.0 ~ 5.0 with the cross-sectional area ratio of side line rectification zone (III).
4. the processing method of a kind of synthesizing ethyl acetate as claimed in claim 1, it is characterized in that described catalyst loading is at reaction zone (II), described catalyzer is cation exchange resin catalyst.
In the present invention, the transformation efficiency of acetic acid is more than 99.8%, and gained ethyl acetate product purity, more than 99.0%, can save energy 20 ~ 40% compared with popular response rectifier unit.
Accompanying drawing illustrates:
Fig. 1 is schema of the present invention.
Embodiment
Below in conjunction with specific embodiment to invention has been further description.
This device comprises rectifying tower (C1), next door tower (C2), phase splitter (1), auxiliary condenser (2), compressor (3), First Heat Exchanger (4), the second interchanger (5).Wherein rectifying tower (C1) and next door tower (C2) are split to form by a complete next door tower, do not establish condenser and reboiler.Next door tower (C2) tower reactor can be divided into three regions with upper part, comprising: rectification zone (I), reaction zone (II) and side line rectification zone (III) of catalyzer are housed.
Phase splitter (1), auxiliary condenser (2), compressor (3), interchanger (5) are installed between two towers, for the auxiliary coupling heat exchange realizing cold and hot logistics.
Processing method of the present invention comprises the following steps:
Step one: ethanol and acetic acid enter next door tower (C2) from the bottom of reaction zone (II), described next door tower (C2) comprises rectification zone (I), reaction zone (II) and side line rectification zone (III), react with Zeo-karb in reaction zone (II) and generate ethyl acetate, the ethanol that the ethyl acetate generated washes away part water through rectification zone (I) and do not react completely, and obtain highly purified ethyl acetate product in side line rectification zone (III) bottom;
Step 2: next door tower (C2) tower top working pressure is 100 ~ 110kPa, service temperature is 60 ~ 75 DEG C, reaction bed temperature is 95 ~ 110 DEG C, still temperature is 115 ~ 120 DEG C, in step one, the tower top of another part water, the ethanol do not reacted completely and portion of ethyl acetate next door tower (C2) forms steam and enters rectifying tower (C1) through compressor (3) pressurization, for it provides upflowing vapor stream, realize the effect of reboiler;
Step 3: described rectifying tower (C1) working pressure is 500 ~ 650kPa, tower top service temperature is 120 ~ 130 DEG C, in rectifying tower (C1), the ethyl acetate generated and water and ethanol define binary, ternary azeotrope, constantly slough the ethyl acetate generated wherein through refinery distillation, obtain the heteroazeotrope stream close to ethyl acetate, water and ethanol at tower top; Most of ethyl acetate of sloughing enters next door tower (C2), obtains highly purified ethyl acetate product in side line rectification zone (III) bottom; Some ethyl acetate of tower top is separated in phase splitter returns to rectifying tower (C1) inside as backflow.
Step 4: at the non-homogeneous mixture stream that rectifying tower (C1) tower top obtains in step 3, through the First Heat Exchanger (4) of next door tower (C2) and the second interchanger (5) and the heat exchange of next door tower (C2) tower base stream, again after auxiliary condenser (2) further cooling, aqueous phase and ester phase is divided in phase splitter (1), aqueous phase discharges system, ester squeezes into rectifying tower (C1) as backflow, at the bottom of the tower of rectifying tower (C1), discharging is as the liquid-phase reflux of next door tower (C2), for next door tower (C2) provides the function of condenser.
Described reaction zone (I) feeding temperature is 20 ~ 80 DEG C, and the raw materials components mole ratio of acetic acid and ethanol is 1: 1 ~ 1.1: 1.
Described next door tower (C2) is 2.0 ~ 5.0 with the cross-sectional area ratio of side line rectification zone (III).
Described catalyst loading is at reaction zone (II), and described catalyzer is cation exchange resin catalyst.
In the present invention, the transformation efficiency of acetic acid is more than 99.8%, and gained ethyl acetate product purity, more than 99.0%, can save energy 20 ~ 40% compared with popular response rectifier unit.
Certainly; the above is only one embodiment of the present invention; should be understood that those skilled in the art; under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications all belong within the protection domain of the claims in the present invention.
Claims (2)
1. a processing method for synthesizing ethyl acetate, is characterized in that comprising the following steps:
Step one: ethanol and acetic acid enter next door tower (C2) from the bottom of reaction zone (II), described next door tower (C2) comprises rectification zone (I), reaction zone (II) and side line rectification zone (III)
Ethyl acetate is generated with catalyst reaction in reaction zone (II), the ethanol that the ethyl acetate generated washes away part water through rectification zone (I) and do not react completely, and obtain highly purified ethyl acetate product in side line rectification zone (III) bottom;
Step 2: next door tower (C2) tower top working pressure is 100 ~ 110kPa, service temperature is 60 ~ 75 DEG C, reaction bed temperature is 95 ~ 110 DEG C, in step one, the tower top of another part water, the ethanol do not reacted completely and portion of ethyl acetate next door tower (C2) forms steam and enters rectifying tower (C1) through compressor (3) pressurization, for it provides upflowing vapor stream, realize the effect of reboiler;
Step 3: described rectifying tower (C1) working pressure is 500 ~ 650kPa, tower top service temperature is 120 ~ 130 DEG C, in rectifying tower (C1), the ethyl acetate generated and water and ethanol define binary, ternary azeotrope, constantly slough the ethyl acetate generated wherein through refinery distillation, obtain the heteroazeotrope stream close to ethyl acetate, water and ethanol at tower top;
Step 4: at the non-homogeneous mixture stream that rectifying tower (C1) tower top obtains in step 3, through the First Heat Exchanger (4) of next door tower (C2) and the second interchanger (5) and the heat exchange of next door tower (C2) tower base stream, again after auxiliary condenser (2) further cooling, aqueous phase and ester phase is divided in phase splitter (1), aqueous phase discharges system, ester squeezes into rectifying tower (C1) as backflow, discharging at the bottom of the tower of rectifying tower (C1) is that next door tower (C2) provides liquid-phase reflux, for next door tower (C2) realizes the effect of condenser;
Described reaction zone (I) feeding temperature is 20 ~ 80 DEG C, and the raw materials components mole ratio of acetic acid and ethanol is 1.1: 1;
Described next door tower (C2) is 2.0 ~ 5.0 with the cross-sectional area ratio of side line rectification zone (III);
The transformation efficiency of described acetic acid is more than 99.8%, and gained ethyl acetate product purity is more than 99.0%.
2. the processing method of a kind of synthesizing ethyl acetate as claimed in claim 1, it is characterized in that described catalyst loading is at reaction zone (II), described catalyzer is cation exchange resin catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104862081B (en) * | 2015-05-06 | 2018-05-08 | 长岭炼化岳阳工程设计有限公司 | Acidification oil esterification prepares the device of fatty glyceride and prepares the method for fatty glyceride using it |
| KR102387476B1 (en) | 2017-11-17 | 2022-04-14 | 주식회사 엘지화학 | Process for Purification of Raffinate-2 streams |
| CN107954866A (en) * | 2017-12-13 | 2018-04-24 | 中国石油大学(华东) | The method and its device of differential pressure heat coupled reaction rectifying synthesis of acetic acid isopropyl ester |
| CN109771980B (en) * | 2018-12-23 | 2021-04-13 | 中国科学院山西煤炭化学研究所 | Heterogeneous azeotropic rectification method for separating mixture of 2-pentanone, 4-heptanone, water and carbon dioxide |
| CN111689836A (en) * | 2020-06-12 | 2020-09-22 | 天津大学 | Methyl acetate hydrolysis process of middle steam compression reaction rectifying tower integrated partition wall tower |
| CN112409172B (en) * | 2020-11-19 | 2023-04-07 | 江门谦信化工发展有限公司 | Method and system for producing ethyl acetate |
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| CN101357887A (en) * | 2008-07-31 | 2009-02-04 | 中国石油大学(华东) | Ethyl acetate synthetic process and apparatus thereof |
| CN101362692A (en) * | 2008-09-24 | 2009-02-11 | 中国石油大学(华东) | Technology method for producing isopropyl trifluoroacetate and apparatus |
| CN102000534A (en) * | 2010-10-02 | 2011-04-06 | 中国石油大学(华东) | Synthesis device of methyl acetate and technological method thereof |
| CN102675093A (en) * | 2012-02-25 | 2012-09-19 | 中国石油大学(华东) | Process for synthesizing n-butyl acetate |
| CN102942475A (en) * | 2012-11-23 | 2013-02-27 | 福建师范大学福清分校 | Variable-pressure rectification method for separating ethyl acetate and ethanol azeotropes and production device for azeotropes |
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2013
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3736236A (en) * | 1970-07-01 | 1973-05-29 | Sir Soc Italiana Resine Spa | Method of separating vinyl acetate from liquid mixtures by extractive distillation with a glycol |
| JPH06336455A (en) * | 1993-05-28 | 1994-12-06 | Showa Denko Kk | Purification of ethyl acetate |
| CN101357887A (en) * | 2008-07-31 | 2009-02-04 | 中国石油大学(华东) | Ethyl acetate synthetic process and apparatus thereof |
| CN101362692A (en) * | 2008-09-24 | 2009-02-11 | 中国石油大学(华东) | Technology method for producing isopropyl trifluoroacetate and apparatus |
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Effective date of registration: 20150707 Address after: Luancheng District of Hebei city of Shijiazhuang Province, Xi Yang Shi 051430 Patentee after: Shijiazhuang Mao Xin Chemical Co., Ltd. Address before: 266580 No. 66 West Changjiang Road, Qingdao economic and Technological Development Zone, Shandong Patentee before: China Petroleum University (East China) |